Destructive hydrogenation of coals, tars, mineral oils, and the like



July 25, 1933. M, MER Er AL 1,919,857 DESTRUCTIVE`HYDROG'ENATIN 0FGOALS, TRS, MINERAL OILS', AND THE LIKE Filed Oct. 6, 1927 TQRNEYSPatented July 2.5, 19u33 UNITED STATES .PATENT oFFlcE MATI-IIAS PIER, OFHEIDELBERG, AND KARL WINKLER, 0F LUDWIGSHAFEN-ON-THE- -RHINE, GERMANY,ASSIGNQES, BY MESNE ASSIGNMENTS, TO STANDARD-I. G. COM- PANY, 0F LINDEN,NEW JERSEY, A CORPORATION 0F DELAWARE DESTRUCTIVE HYDROGENATION OFGOALS, TABS, MINERAL OILS, AND THE LIKE Application iled October 6,1927, Serial No. 224,519, and in Germany October 14, 1926.

The present invention relates to the destructive hydrogenation ofcarbonaceous materials, i. e. the production -of valuable liquid orother hydrocarbons or derivatives thereof by treating carbonaceousmaterials, such as solidand liquid fuels,distillation or extractionproducts thereof and the like, with gases containing or giving rise tohydrogen at elevated temperatures and preferably under pressure With orWithout the aid of catalysts. v

We have found that the said process can be carried out with specialadvantage with suoli gases as are obtained by decomposing gases orvapors containing gaseous hydrocarbons at temperatures above 900 C.byinteraction with such quantities of substantially pure carbon dioxidethat the hydrocarbons are converted mainly into carbonmonoxide andhydrogen. All or part of the carbon monoxide formed may be subsequentlydecomposed catalytically into carbon dioxide and hydrogen by means of'Water vapor.

The decomposition of the hydrocarbons is advantageously carriedl out inthe presence of catalysts which may be' solid as, for example, magnesiawith nickel precipitated thereon, such as molten iron o r alloysthereof.

Preferably the gas mixture rich in hydrocarbons resulting from thedestructive hydrogenation of carbonaceous materials is employed as theinitial gas for the decomposition describedabove. It may be desirable toseparate valuable compounds, for example the higher ,hydrocarbons suchas ethane, propane and the like, from the gases,if contained in them,p)rior to their decompositiom-for instance, y coolmg to low temperaturesor by means of Vporous adsorbents, and toutilize the said compounds forexample for chemical purposes, stance to chlorinate them or to oxidizethem to formaldehyde and the like or to convert them at elevatedtemperatures into oleines, from which other valuable comj pounds can' bemanufactured. Water vapor may be added to the carbon dioxide. Ifconsiderable quantities of water alytically active.

or iron alloys or liquid,

thereof may sometimes be dispensed With.

The mixture of gases containing hydrocarbons and carbon dioxide isheated to at least QOOOKC. but preferably to 11000 C. or even highertemperatures. Vhen adding air to the said mixture, part of the heatneeded is produced by the partial combustion of the hydrocarbons, orother combustible gases contained in the mixture. The decomposition isvery advantageously effected in a shaft furnace of high thermalcapacity, lined with refractory materials and filled with refractorymasses, the said furnace being heated up by the combustion of anycombustible gas with oxygen or air. Thehcating gas may also be replacedby vaporized oil or pulvei'ized coal. The refractory material employedmay also be cat- The shaft furnace may also 'be filled With coke insteadof with refractory material, and operated as a pro ducer. In this case,the gases containing hydrocarbons to be decomposed are introduced withcarbon dioxide and, if required, With steam or other gases, in the coldblowing stage. The .gases of the heating blast stage may be utilized inother Ways, example, for the production of nitrogen for the syntheticmanufacture of ammonia.

The requisite carbon dioxide is preferably separated from industrialWaste gases.

The invention Will be further illustrated withv reference to theaccompanying drawving showing iny a diagrammatic fashion a.

hydrocarbons.

Referring to this drawing in detail hydro-- carbon gas issuing from adestructive hydrogenation plant (not shown) is supplied by way of pipe1, valve 2 and pipe 3 into the vessel 4 4heated to a temperature ofabout for '1100 C. and filled with a suitable refractory.

material. At the same time carbon dioxide is introduced into lthisvessel by'way of valve 5 and pipe 6. The hydrocarbon gas may also bemixed with the carbonv dioxide before entering into the vessel '4. Inthis case valve 2 is shut off and the hydrocarbon gas passes throughvalve 7 and :intermingles with the carbon dioxide in pipe 6. In vessellthe simultaneous formation of hydrogenfrom steam. The gases leaving vthevessel- 10 at 13 are passed through the condenser 12 in which the mainpart of the superiuous steam is condensed.y The condensedvwater iscollected in separator 1&4 and may be withA drawn at 15. he uncondensedvgases v are then passed through a vessel 16 in Whieh the carbon dioxidecontained inlsaid 'gases may be removed therefrom by washing underpressure with a suitable solvent. The gas freed' from carbon dioxideymay be passed back to the hydrogenating plant by Wa of plipe 17.

.''he fo owing example will further 1ll us trate how the said inventionmay be carried Blf into practical effect but the invention isnotlimitedA thereto.

Ewwmple A gas containing 30 to 40 per cent df .methane and4 obtainedinthe-'destructive hydrogenation of coals, tars, or mineral oils at anelevated tem erature and under pressure, is mixed with) an amount ofsubstantially pure carbon dioxide corresponding tothemethane content, sothat a gas mixture having, for example, the composition .CO2 23.6 percent, H2 52 per cent, CH.4 22.5 per cent, N2 1.3per cen't andCO 0.6 percent is formed. This gas is passed at a temperature of about 1100centigrade through a shaft funnace 'lined with refractory material andfilled with refractory masses on which metals with catalytic properties,such. as nickel, have been deposited if desired.

The furnace is heated up, for example, by-burning a gas obtained'in theaforesaid destructive hydrogenation land having the following aproximate 'compositions-C 10per cent, Il; 6 per cent, CO2 0.8 per cent,the remainder being hydrogen. A portionv of the gas mixture which is tobe converted, and has thecomv ositon specified above, may also beemploye as the heating' agent.

On passlng the aforesaid initial gas mixture over the highly heatedrefractory`ma- "the step which comprises gas lssu-ing from the saidhydrogenation and obtained teria'l, a gas 'mixture containing CO 31.4per' cent,l H2 66.2 -per cent, 0021.1 per cent and N2. 1.3 per cent isobtained. By treatment with steam at about 500. centigrade` and underany'convenient pressure, the car- .bonaceous substances. such as solidiand liquid fuel, distillationf'and extraction products thereof, intovaluable liquid and other hydrocarbons and derivatives thereof bytreatment with a gas' containing hydrogen, the stepwhich comprisessubjecting waste gas issuing from the saidhydrogenation and gaseoushydrocarbons tojdecorn 4interaction vwith a gas essenticarbon dioxide insuch an /containin position 'ally lcontalnin amount that convertedmainly. into hydrogen and carbon monoxide .by reaction with said carbondioxf ide 'at a temperature above l900o C. and. using the gasthusobtained in the said hydrogenaf tion.

2. yIn the. destructive hydrogenation of car-v bonaceous substances suchasv solid and liquid fuel, distillation and extraction products thereof,into valuable liquid and other hydrocarbons and derivatives thereof bytreatment With agas-containing hydrogen, step which comprises subjectingwaste gas issuing from 'the said hydrogieriation and containing gaseoushydrocarbons to decomposition by interaction with a gas -essenltiallycontaimng carbon dioxide in` such an amount that the aseous hydrocarbonsare converted mainly 1n'to hydrogenand carbon monoxidefby reaction withsaid carbondioxide at a temperature above `900" C., 'converting the"carbon monoxide v formed i by means of steam intofcarbon dioxide andhydrogen, removing the carbon. dioxide and egaseousl hydrocarbons areusing the gasl thus obtained in the'said hydrogenation. 4 f l '3. In thedestructive hydrogenation of `carbonaceous substances such as solid andliquidfuel, distillation and extraction products thereof, intovaluableliquid and other hydrocarbons `and ,derivatives thereof by treatmentwith; a gas containingh'ydrogen subjecting waste convert thehydrocarbons mainly into -h drogen and carbon monoxide, conver ting t ecarbon monoxide formed by means. of steam the carbon dioxide and using`the gas thus the said hydrogenation.'

' into carbon dioxide and hydrogen, removing- 4. In the destructivehydrogenation of carbonaceous substancesV such as solid and liquid fuel,distillation and extraction products thereof, into valuable liquid andother hydrocarbons and derivatives thereof by treatment With a gascontaining hydrogen, the step which comprises passing waste gas issuingfrom the said hydrogenation and containing gaseous hydrocarbons with agas essentially containing carbon dioxide in such an amount that thegaseous hydrocarbons are converted mainly into hydrogen and carbonmonoxide by reaction with said carbon dioxide over refractory massesheated to above 900 C., convertin the carbon monoxide formed by means osteam into carbon dioxide and hydrogen, removing the carbon dioxide andusing the gas thus obtained in the said hydrogenation.

5. vIn the 4destructive hydrogenation of carbonaceous substances such assolid and liquid fuel, distillation and extraction products thereof,into valuable liquid and other hydrocarbons and derivatives thereof bytreatment with a gas containing hydrogen,

the step which comprises passing Waste gas issuing from the saidhydrogenation and containing gaseous hydrocarbons with a gas essentiallycontaining carbon dioxide in such an amount that the gaseoushydrocarbons are converted mainly into hydrogen and carbon monoxide byreaction with said carbon dioxide over refractory .masses heated toabove 900 C. and carrying nickel, convertingthe carbon monoxide vforinedby means of steam into carbon dioxide and hydrogen, removing the carbondioxide and using the gas thus obtained in the said hydrogenation.

6. In the destructive hydrogenation of carbonaceous substances such assolid and means of steam into carbon dioxide and hydrogen, removingthecarbon dioxide and using the gas thus obtainedI in the said hy-vdrogenation.

7. In the destructive hydrogenation of carbonaceous substances such assolid and liquid fuel, distillation and extraction products thereof,into valuable liquid and other hydrocarbons and derivatives thereof bytreatment with a gas containing'hydrogen, the step which comprisessubjecting waste gas issuing from the said hydrogenation and containing'gaseous hydrocarbons to decom- A position kby interaction with a gasessentially containing carbon dioxide in such an `amount that thegaseous hydrocarbons are converted mainly into hydrogen and carbonmonoxidev by reaction with said carbon dioxide at ay temperature above900 C., steam being added with said gas to convert the carbon monoxideformed into carbon dioxide and hydrogen, removing the carbon dioxide andusing the gas thus obtained in the said hydrogenation.

MATHIAS PIER. KARL WINKLER.

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